Washing, wetting, and emulsifying agent



Patented May 19, 1942 Lucas P. Kyrldes, Webster Groves, Mm, assignor toMonsanto Chemical Comp ny, St. Louis, Mo., a corporation of Delaware NoDrawing. Application December 24, 1937, Serial No. 181,597

' 16 Claims. (01.252-89) The present invention relates to wettingagents, emulsifying agents, textile assistants, detergents and similaragents and refers particularly to new agents of this class. The agentsare the salts of acids resulting from the reaction of unsaturatedhydrocarbons, alkyl chlorides or alcohols with maleic anhydride andsimilar aliphatic carboxylic acids or anhydrides containing the'alpha-betaenal grouping,

-c=cc=o l 'l I The present invention is based upon my discovery thatalkali metal salts of the carboxylic acids obtained by the addition orcondensation of mono-olefins, alkyl chlorides and alcohols containinfrom five to sixteen carbon atoms in the molecule, such as diisobutyleneand triisobutylene, with various unsaturated aliphatic acids possessingthe alpha-beta-enal grouping are characterized by pronounced wettingaction. These compounds are comparable in their surface activity tosimilar well-known wetting agents such as the sulfated alcohols and thesulfonated alkyl aromatic hydrocarbons commonly used for this purpose,especially in their action in hard water, but many of them do not foamor lather as readily when mixed in water in the manner that is typicalof known wetting agents. This failure to foam is a definite advantagefor certain purposes, and does not detract from their desirability aswetting agents or detergents.

The condensed acids which I have found desirable for use in my inventionare those derived from the reaction of unsaturated carboxylic acidscontaining the alpha-beta-enal grouping with mono-olefins containingabout five to sixteen carbon atoms per molecule. Such olefins are thevarious amylenes, hexylenes, heptylenes or mixed olefins which result asby-products in petroleum cracking operations or as by-products in thechlorination of saturated aliphatic hydrocarbons. The olefins may bepolymers of lower hydrocarbons, for example, diisobutylene or mixedisomeric triisobutylenes, which result from polymerization ofisobutylene with sulfuric acid or metallic halides or result fromsimultaneous dehydration and polymerization of tertiary-butyl alcohol byconcentrated sulfuric acid.

The olefins are added to or condensed with aliphatic carboxylic acids oranhydrides containing the alpha-beta-enal grouping. Unsaturated acids ofthis type are fumarlc or maleic acid, HO0C-CH=CHCOOH, itaconic acid,CHz=C(COOI-I)CH:COOH, citraconic acid, CHaClCOOH) =CHCOOH, acrylic acid,

and crotonic acid, CHaCH=CH-COOH. Because of their case of condensationand since they are readily obtainable, the anhydrides of dicarboxylicacids of this series are preferred as the starting materials for theaddition or condensation reaction to produce the compounds contemplatedin the invention. Maleic anhydride is the most common and most readilyavailable acid anhydride of this series and hence is particularlyconsidered throughout this specificaton. Aromatic acids such as phthalicacid, in which the reactive portion of the alpha-beta-enal grouping ispartly incorporated in the phenyl nucleus, are not operative.

The reaction by which the compounds of the invention are obtained isconsidered to take place by addition of the'olefin at the double bond ofthe unsaturated dicarboxylic acid. As far as can be determined, theunsaturation of the original olefin reacted is preserved. The reactionof maleic anhydride withdiisobutylene and its subsequent hydration withwater is representable as:

The product is an octene-succlnic acid, viz., dilsobutylene-succinicacid, or, when other olefins are used, in general, an alkene-succinicacid.

The reaction itself is referred to herein either as an addition orcondensation reaction, since, as will be pointed out hereinafter, alkylhalides yield products by elimination of hydrogen chloride that aresubstantially identical with those obtained from olefins. Alcoholsundergo a similar reaction by addition of'the alcohol at the double bondofthe acid. The reaction of olefins and unsaturated acids is describedin U. S. Patent' 2,055,456;

The condensation of the olefin with the unsaturated acid containing thealpha-betaqenal grouping can be conducted with stirring under {reflux orpressure to avoid any loss of volatile materials. sBy conducting thereaction under pressure the period of heating can be somewhat reduced.At atmospheric pressure periods as long as 48 hours or more of heatingat a temperature sufficient to maintain a gentle reflux are required. Ofcourse, with amylene and similar low-boiling olefins the temperaturerequired to maintain a reflux is too low to produce any appreciablereaction, hence autoclaving or pressure treatment is desirable. However,refluxing at atmospheric pressure can be used with mixtures that refluxat about 150 C. or above. For example, in heating triisooutylene withmaleic anhydride, gentle refiuence at the beginning of the reaction canbe maintained by keeping the mixture at about 156 C. As reactionprogresses higher temperatures are required to maintain the reflux. Byconducting the reaction in this manner, viz.,.by raising the temperatureof heating just sufficient to maintain a gentle reflux, the end of thereaction can be judged as that point at which no further rise intemperature of the mass is required to maintain refluence. No such guideis available, of course, when the reaction is conducted in an autoclaveunder pressure and in that case some preliminary experimentation isrequired with each individual reaction mixture to determine the optimumperiod of reaction under the particular conditions. The period ofreaction will be dependent upon the pressure maintained as well as thetemperature and -can be controlled'by varying both.

The proportions of reacting materials may be varied. Theoretically,equimolecular quantities of the acid and olefin combine. Generally whenequimolecular quantities are used the reaction does not proceed tocompletion and to facilitate it, it is preferable to add an excess ofone reactant. When reacting the mass under pressure I prefer to use anexcess of olefin since it is easily recoverable but when conducting thereaction under atmospheric pressure I prefer to use an excess of theacid to permit maintaining a higher temperature during the heating ofthe reaction mass.

From the resulting reaction mixture, for example, that resulting fromtriisobutylene and maleic anhydride, which is a viscous fluid mass, theunreacted olefin or acid may be recovered by any of the usual methods.After reacting maleic anhydride With triisobutylene, I prefer to add tothe mass a solution of sodium hydroxide, whereupon the excess olefinseparates as a supernatant layer. The acid that has formed dissolves inthe aqueous layer in the form of the respective sodium salt. The aqueouslayer after separation is then acidified to precipitate thetriisobutylene-succinic acid formed as a result of the reaction whilethe unreacted maleic aci'd remains in solution. Be-

1 fore separating the precipitated acid mass from the aqueous solutionit is advantageous to add a water-immiscible solvent such as chloroformto the mixture to reduce the viscosity and take up thetriisobutylene-succinic acid remaining dissolved in the maleic acidaqueous layer. The two layers are then separated, the acid product isrecovered from the chloroform layer, and the products in the aqueouslayer also are recovered. Obviously, other methods may be used for theseparation.

The separation may be dispensed with after merely removing unreactedolefin, for example, by distillation in vacuum or with steam, inasmuchas small amounts of unreacted maleic or other from the decomposition ofalkyl chlorides.

acid which may be present generally have no detrimental effect in theparticular contemplated use.

Instead of using diisobutylene, triisobutylene and, similar olefinsresulting from polymerization of refinery waste gases, I may use olefinsresulting Thus, decyl chloride, dodecyl chloride and tridecyl chlorideobtained by chlorinating the corresponding paraflin hydrocarbons orpetroleum fractions rich therein can be converted to the correspondingolefinsby heating. This decomposition may be advantageously facilitatedby catalysts. The decomposition to olefins may be eifected in thereaction mixture with the maleic anhydride, that is, instead of reactingthe olefin and the maleic anhydride, the alkyl chloride may be reacteddirectly with the maleic anhydride. The products correspond in formulaand properties to those obtained from the respective olefins.

The resulting triisobutylene-succinic acid or similar acid product isthen converted to the sodium salt or other alkali-metal salt by means ofsodium hydroxide or other alkali hydroxide. The potassium salts of thecompounds of the invention possess the same general characteristics asthe sodium salts. Alkali-metal salts of the acids are replaceable by thefree acids themselves or by salts of the acids'with ammonia or organicbases. Thus, salts with ammonia, triethanolamine, mono-, di-, ortri-ethyl amine, etc., pyridine, nicotine and the like, can be prepared.The salts with nicotine are insecticidal in nature and permit the use ofthis material in aqueous media and furthermore, provide compositions ofincreased spreading power. The alkene-dicarboxylic acid may also bepartially esterified, for example, the monoethyl ester oftriisobutylene-succinic acid, and the salt of the partially esterifiedacid used in a similar manner.

Instead of reacting anhydrides of dicarboxylic acids I may use the acidsthemselves, but in this event the addition or condensation reactionproceeds somewhat more slowly than with the anhydrides. Withmonocarboxylic acids and acids that do not form anhydrides no choice'inthis regard exists. Maleic acid may be replaced by its isomeric form,fumaric acid.

To the salts of the invention various adjuvants or builders may beadded, for example, such materials as sodium carbonate, sodium sulfate,magnesium sulfate, etc., particularly when the products are to be usedas detergents. When sodium carbonate is used in this manner the freeacid instead of its sodium salt may be incorporated into thecomposition, since the sodium carbonate converts the acid to the salt inaqueous solution and thus obviates the step of converting the free acidto the salt.

The compounds of the invention are of value in the preparation ofdetergents, polishes, wax and hydrocarbon oil emulsions, insecticidalemulsions, cold water paints and as thickening agents for rubber latex,as flotation reagents, as pigment treating agents to improvedispersibility and grinding properties, as rubber compoundingingredients and the like. They are of especial value i or thepreparation of detergents for use in hard water, for which purpose theyare equal to or superior to sulfonated detergents such asalkylbenzenesulfonic acids. The calcium salts of the compounds aresoluble in water, and the compounds are well-adapted for use in alkalineWashing operations. By the term wetting agent" as used in thespecification and claims is to be understood an agent suitable for useas adetergent, emulsifying agent, textile assistant, dispersing agent,etc., or, in general, agents whose properties of reducing surfacetension of liquids make them eminently desirable for many applicationsdependent upon their surface activity.

In place of alkene-substit'uted acids resulting from condensation of anolefin with an unsaturated aliphatic carboxylic acid containing thealpha-enalgrouping (as shown below as Formula I) I may use similarcompounds which are satu-, rated alkoxy-substituted acids, for example,lauroxy-succinic acid, or in general, as typified by Formula IIhereinbelow:

Alkenyl-H (J-C O O H I. Alkene-acids Alkanyl-O-H(i3COOH II. Alkoxy-acidsIn both these formulae the grouping -HCC OH must correspond to thatwhich would result from an unsaturated aliphatic acid containing theessential alpha-beta-enal grouping, for example, the grouping may bethat found in succinic acid (resulting from saturation of the maleicacid double bond), propionic acid (saturation of acrylic acid doublebond), or pyrotartaric acid or methyl succinic acid (saturation ofdouble bonds in itaconic or citraconic acids). These alkoxy-acids areconsidered as condensation products of an alcohol and an'unsaturatedaliphatic carboxylic acid characterized by the presence of thealpha-beta-enal grouping. The wetting properties of the alkoxy-acids,like those of the alkene-acids are dependent upon the length of thechain, and alkoxy-acids having chains containing from five to sixteencarbon atoms are effective wetting agents.

In preparing the alkoxy-acids represented above in the general FormulaII, various methods are available. In my preferred methods, however, Iprefer to start with an alcohol and an ester of the unsaturated acid,that is, to prepare lauroxy-succinic acid, lauryl alcohol and diethylmaleate are condensed in the presence of metallic sodium under anhydrousconditions. The resulting diethyl ester of lauroxy-succinic acid issaponified and thesalt formed after saponification is then converted tothe acid.

Instead of starting with diethyl maleate I may start with the halfester, monoethyl maleate, by forming the sodium salt-of the half esterand reacting this salt with lauryl alcohol under anhydrous conditionswith metallic sodium. Saponification of the resulting salt and recoveryas before, yield lauroxy-succinic acid.

Alcohols containing from five to sixteen carbon atoms can be thusreacted to product salts of acids having efiective wetting properties.Such alcohols include amyl alcohols, hexyl alcohols, heptyl alcohols,octyl alcohols, decyl alcohols, dodecyl (lauryl) alcohols and hexadecyl(palmityl) alcohols.

The following examples are illustrative of the method of preparing thecompounds of the invention:

EXAMPLE l.-Triisobutylene-succinic acid.- Two hundred fifty-two grams oftriisobutylene (B. P.165-1'75" C.) were refluxed with 98 grams of maleicanhydride while agitating. Refiuence started at a temperature of 157 andwas maintained by gradually increasing the temperature over a period of80 hours to 193 C. An additional 20 hours of heating failed to produceany further elevation of the temperature of refiuence. The reactionproduct was dissolved in 5% sodium hydroxide solution and the unreactedolefin was separated. The remaining liquid was made acid to Congo redindicator by the addition of 1% hydrochloric acid solution. Extractionof acid and water layers with chloroform and subsequent evaporation ofthe solvent yielded triisobutylenesuccinic acid. The product was in theform of a dark, gummy, resinous mass. The approximate content of thedesired product can be determined by titrating a sample of the productto a thymol blue end-point with N/2 sodium hydroxide solution andcalculating on the assumption that all titratable material istriisobutylenc-succinic acid. The salt was prepared by adding sodiumhydroxide solution in quantity just sufficient to neutralize the acid,according'to the titration results. By dilution with water, solutions ofthe sodium salt of desired concentration may beprepared for use or thesodium salt may be recovered by evaporation or other suitable methods.

' EXAMPLE 2. DecyZene-succinic acid-Onefifth mol (35.3 grams) of decylchloride obtained by chlorinating a commercial petroleum decane fractionwasheat-ed under reflux with one-fifth mol grams) of maleic anhydride.'Evolution of hydrogen chloride started at 176 C. Refluxing started at178 C. The vapor temperature did not gradually "rise as observed whencondensing olefins with maleic anhydride. Heating was discontinued atthe end of 50 hours, at which time evolution of hydrogen chloride hadpractically ceased. The reaction product was made alkaline with 5%sodiumhydroxide solution ands the light, oily fraction of decyl chloride wasseparated. The sodium salt solution was made acid to Congo red with 10%hydrochloric acid solution and the precipitated acid was separated fromthe aqueous solution. The acid and water layers were thoroughlyextracted with chloroform. Evaporation of the chloroform extractsyielded a dark, gummy mass. This product assayed decylene-succinic acidby the method described in Example 1. The sodium salt or its solutioncan be prepared by the method described in Example 1.

EXAMPLE 3.Triisobutylene-succi1iic acid.- Into a one-liter steelautoclave were charged 500 grams of triisobutylene and 150 grams ofmaleic anhydride. The mixture was heated to 208 C. for 3 hours withagitation. The pressure developed ranged from to pounds per square inch.The products were treated with a 5% excess of dilute sodium hydroxidesolution over that required to neutralize the maleic anhydride charged.This solution was refluxed for 2 hours and subsequentlycooled. Twolayers of liquids resulted,the supernatent layer of triisobutylene wasseparated and discarded. The aqueous layer was made acid to Congo redpaper with concentrated hydrochloric acid. The acid and water portionswere extracted with chloroform. The free triisobutylene-succinic acidobtained on evaporation of the chloroform can be converted to the sodiumsalt as described in Example 1.

EXAMPLE 4.Lauroa:y-succinic acid. -Three hundred forty-four grams ofdiethyl maleate (approximately 2 mols) and 410 grams of lauryl alcohol(approximately 2.2 mols) were placed in a conditions.

flask provided with a reflux condenser. Approximately 5 grams (0.2 gramatoms) of sodium metal (in small pieces or in rolled form) were thencontinuously added. Reaction started immediately and the mixture becamewarm- The mixture was allowed to stand until the initial reaction.subsided and was thereupon heated on a steam bath for several hours. Tothe mixture was then added alcoholic sodium hydroxide in quantitysuflicient to .saponify the ester and the mixture was subjected torefluxing. After saponification was complete the mixture was cooled,ethyl alcohol w'asgdistilled from the mixture and unreacted laurylalcohol was extracted from the alkaline solution with a non-aqueoussolvent. The reaction mixture was then made acid with hydrochloric acidand the precipitated lauroxysuccinic acid was removed by extraction withchloroform. The residual solution contained maleic acid resulting fromunreacted diethyl maleate. The lauroxy-succinic acid was converted toits sodium salt and recovered as such.

The free lauroxy-succinic acid is a solid of waxy appearance and itssodium salt is a mass resembling soap in appearance and feel.

Wetting tests-The sodium salt of triisobutylene-succinic acid formed inExample 1 was dissolved in water to make solutions of varying dilutions.Similarly, solutions of a commercial wetting agent know n to thetradeunder the mark Santomerse, which is a sodium sulfonate, were made. Thesesolutions were tested for wettability by placing a cotton thread in eachand determining the period it took for the thread to become completelywetted by the solution. In some cases a small proportion of hydrochloricacid was added to the solution. The tests with both materials wereconducted under exactly comparable The periods required for'wetting atthe various dilutions are as indicated in the table:

Sodium salt Standard soil launderometer tests-Standard soillaunderometer tests were made with the sodiumsalts oftriisobutylene-succinic acidpre pared in Example 1 and thelauroxy-succinic acid prepared in Example 4, in comparison underidentical conditions with the commercial detergent Santomerse.Thestandard soil washing test is conducted as follows: To a desiredcotton fabric is applied under controlled conditions a standard soilsolution. This solution is composed or a suspension'of carbon black,vegetable oils and mineral oils in water. The fabric is then aged for apredetermined period. The aging of the fabric is important because thesoil is more difficult to remove as it becomes older; 'I'he'soiledfabric is then washed in a launderometer and each sample is tested intriplicate at various wash intervals 10, 20, 30 and 40 minutes aresuitable).

The washed sample is then dried and the lightening of the fabricis'determined, using a Pulfrich photometer. v The relative detergency isthen established.

The table illustrates the improvement in whiteness expressed as per centbaryta white units obtained with the detergents when used in both hardand in soft water.

fi lfi it? sa r ss 0 55259, isobutyllauroxyene supcinic suocimc acidacid 8 5 9 l5 7 ll 18 9- 13 21 l1 14 Hard water (300 PPM):

1st wash min.) 13 12 2nd wash min.) l7 l8 3rd wash min.) 18 21 4th Washmin.) 20 24 from the invention, which is defined in the ap pendedclaims. Iclaim: 1. A washing, wetting and emulsifying agent comprising awater-soluble salt of a condensation product of an unsaturated aliphaticcarboxylic acid containing the alpha-beta-enal grouping with a compoundselected from the group consisting of aliphatic mono-olefins and alkylchlorides containing at least five and less than seventeen carbonatoms'in the molecule.

2. A-washing, wetting and emulsifying agent comprising an alkali-metalsalt of the condensation product of maleic anhydride and an aliphaticmonoolefin containing from five to six- I teen carbon atoms in themolecule.

-3. A washing; wetting and emulsifying agent comprising an alkali-metalsalt of the reaction product of maleic anhydride and an alkyl chloridecontaining from five to sixteen carbon atoms in the molecule.

' 4. A washing, wetting and emulsifying agent comprising a water-solublesalt of a condensation productiof an unsaturated aliphatic carboxylicacid containing the alpha-beta-enal grouping with a compound selectedfrom the group consisting of aliphatic mono-olefins and alkylchloridescontaining at least five and less than seventeen carbon atoms in themolecule, which'condensation product consists of a carboxylicacidcorresponding to the general formula in which 'R is selected fromthe group consisting of hydrogen, carboxyl and lower alkyl radicals andin which the alkenyl group containsat least five and less than seventeencarbon atoms in the molecule.

5. A washing, wetting and emulsifying agent comprising a water-solublesalt of a condensation product of an unsaturated aliphatic carboxylicacid containing the alpha-beta-enal grouping with diisobutylenawhichcondensation product consists of a carboxylic acid corresponding to thegeneral formula H Alkenyl-(k-C O OH 9. A wetting and detergentcomposition for the treatment of textiles, which comprises an aqueoussolution of more than about 0.125 part of a water-soluble salt of acondensation product as 5 defined in claim l per hundred parts of water.R-C-R 10. A' washing, wetting and emulsifying agent comprising thesodium salt of the condensation in which R. is selected from the groupconsisting of hydrogen, carboxyl and lower alkyl radicals and in whichthe alkenyl radical is that resulting from diisobutylene.

6. A washing, comprising a water-soluble salt of a condensation productof an unsaturated aliphatic carboxylic acid containing thealpha-beta-enal grouping with triisobutylene, which condensation productconsists of a carboxylic acid corresponding to the general formulawetting and emulsifying agent product of maleic anhydride anddiisobutylene. 11. A washing, wetting and emulsifying agent comprisingthe sodium salt of the condensation product of maleic anhydride andtriisobutylene.

12. The process of washing textiles which comprises agitating saidmaterials while they are immersed in an aqueous solution of awatersoluble salt of a condensation'product as defined in claim 1.

13. The process of washing textiles which comprises agitating saidmaterials while they are immersed in an aqueous solution of an alkali- H20 metal salt of the condensation product defined in Alkenyi-l-COOHclaim 14. The process of washing textiles which comprises agitating saidmaterials while they are sation product of maleic anhydride anddiisobutylene.

8. A washing, wetting and emulsifying agent comprising an alkali-metalsalt of the condensation product ofmaleic anhydride and triisobutylene.

Patent No. 2,283,211,-

LUCAS 'P KYRIDES immersed in an aqueous solution of an alkalimetal saltof the condensation product defined in claim 8.

prises agitating said materials while they are immersed in an aqueoussolution of the sodium salt of a condensation product as defined inclaim 11.

.LUCAS, P. KYRIDES.

CERTIFICATE 6F (JGRREEIT 0N M y s 9 m.

It is hereby-certified that error appears in the printed specificationof the above numbered patent requiring correction as follows: Page l,-second column, line 55, for"C H read -C H page}, first column, line614., for "product" read --produco--; and that the said Letters Patentshould be read with this correction therein that the same may conformtothe rec ord of the case in the Patent Office.

Signed. and. sealed this 50th day of June, A. D. 19Li2.

' Henry Van Ar'sdale, Acting commissioner of Patents.

(Seal) Patent No. 2,283,21Lp

CERTIFICATE dF'cdmc'rct'on.

. May 19 1913, LUCAS P. mamas.

It is hereby-certified that error appears in the printedepecificatioa ofthe above numbered patent requiring correction as follows: Page 1,second column, line 55, for"'C H read --C H page 5, first column, line Ifor "product" read --produce-- and that the said Letters Patent -shouldbe read with this correction therein that the same may conform to therecord of the case in the Patent Office.

Signed. andsealed this 30th day of June, A. n. 1912.

. Henry Van Arsdale, (Seal) Acting Commissioner of Patente.

